Supporting Information. Experimental section

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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Supporting Information Experimental section General. Proton nuclear magnetic resonance ( 1 H NMR) spectra were recorded with a Varian Mercury plus (400 MHz) spectrometer. Chemical shifts are reported in delta (δ) units, part per million (ppm) downfield from trimethylsilane. Coupling constants are reported in Hertz (Hz). Carbon-13 nuclear magnetic resonance ( 13 C NMR) spetra were recorded with a Varian Mercury plus (100 MHz and 125 MHz) spectrometer. Chemical shifts are reported in delta (δ) units, part per million (ppm) relative to the center of the triplet at ppm for deuteriochloroform. Representative procedure for the reaction: A mixture of cinnamyl alcohol (67.1 mg, 0.5 mmol), 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene (Imes, 15.2 mg, mmol), 2,2,6,6-tetramethylpiperidine N-oxy (TEMPO, mg, 0.5 mmol) and hexafluoroisopropyl alcohol (HFIP, 10.5 mg, 0.1 mmol) in toluene (0.5 M, 1 ml) was equipped with a seal tube and stirred at 100 C for 18h under air atmosphere. The reaction mixture was evaporated and purified by flash silica gel column chromatography by using 1% ethyl acetate/hexane to obtain cinnamyl cinnamate 1b (58.5 mg, 89 %).

2 Cinnamyl cinnamate (Table 1, 1b) : The representative experimental procedure was applied to cinnamyl alcohol 1a (67.1 mg, 0.5 mmol) to yield 1b (58.5 mg, 89 %). 1 H NMR (400 MHz, CDCl 3 ): 7.73 (d, 1H, J = 16.0 Hz), 7.52 (m, 2H), (m, 8H), 6.70 (d, 1H, J = 15.6 Hz), 6,48 (d, 1H, J = 16.0 Hz), 6.35 (m, 1H), 4.87 (d, 2H, J = 6.8 Hz) ppm 13 C NMR (100 MHz, CDCl 3 ): 166.7, 145.1, 136.3, 134.4, 134.3, 130.4, 129.0, 128.7, 128.2, 128.1, 126.7, 123.4, 118.0, 65.4 ppm IR (neat, cm -1 ): 3027, 2360, 1713, 1637, 1166 HRMS: C 18 H 16 O 2 Cacld : , [M] + Found :

5 (E)-(E)-3-(4-methoxyphenyl)allyl 3-(4-methoxyphenyl)acrylate (Table 4, 2b) : The representative experimental procedure was applied to (E)-3-(4-methoxyphenyl)prop-2-en-1- ol 2a (82.1 mg, 0.5 mmol) to yield 2b (67.7 mg, 84 %). 1 H NMR (400 MHz, CDCl 3 ): 7.69 (d, 1H, J = 16.0 Hz), 7.48 (d, 2H, J = 8.4 Hz), 7.36 (d, 2H, J = 8.8 Hz), 6.89 (m, 4H), 6.66 (d, 1H, J = 15.6 Hz), 6.36 (d, 1H, J = 16.0 Hz), 6.24 (m, 1H), 4.85 (d, 2H, J = 6.8 Hz), 3.80 (d, 6H, J = 8.8 Hz) ppm 13 C NMR (100 MHz, CDCl 3 ): 167.0, 161.3, 159.5, 144.6, 133.9, 129.8, 129.1, 127.9, 127.1, 121.2, 115.5, 114.4, 114.1, 65.4, 55.5 (2C) ppm IR (neat, cm -1 ): 2936, 2360, 1708, 1513, 1161 HRMS: C 20 H 20 O 4 Cacld : , [M] + Found :

8 (E)-(E)-3-(p-tolyl)allyl 3-(p-tolyl)acrylate (Table 4, 3b) : The representative experimental procedure was applied to (E)-3-(p-tolyl)prop-2-en-1-ol 3a (74.1 mg, 0.5 mmol) to yield 3b (53.5 mg, 73 %). 1 H NMR (400 MHz, CDCl 3 ): 7.71 (d, 1H, J = 15.6 Hz), 7.43 (d, 2H, J = 8.0 Hz), 7.31 (d, 2H, J = 8.0 Hz), 7.20 (d, 2H, J = 7.6 Hz), 7.14 (d, 2H, J = 8.0 Hz), 6.68 (d, 1H, J = 15.6 Hz), 6.44 (d, 1H, J = 16.0 Hz), 6.32 (m, 1H), 2.37 (d, 6H, J = 12.4 Hz), 2.18 (s, 2H) ppm 13 C NMR (100 MHz, CDCl 3 ): 166.9, 145.1, 140.8, 138.0,134.3, 133.6, 131.8, 129.7, 129.4, 128.2, 126.6, 122.4, 117.0, 65.4, 31.2, 21.8, 21.6 ppm IR (neat, cm -1 ): 3025, 1713, 1636, 1514, 1162 HRMS: C 20 H 20 O 2 Cacld : , [M] + Found :

11 (E)-(E)-3-(4-chlorophenyl)allyl 3-(4-chlorophenyl)acrylate (Table 4, 4b) : The representative experimental procedure was applied to (E)-3-(4-chlorophenyl)prop-2-en-1-ol 4a (84.3 mg, 0.5 mmol) to yield 4b (67.2 mg, 81 %). 1 H NMR (400 MHz, CDCl 3 ): 7.67 (d, 1H, J = 15.6 Hz), 7.45 (m, 2H), 7.31 (m, 6H), 6.65 (d, 1H, J = 16 Hz), 6.45 (d, 1H, J = 15.6 Hz), 6.32 (m, 1H), 4.86 (d, 2H, J = 6.0 Hz) ppm 13 C NMR (125 MHz, CDCl 3 ): 166.4, 143.7, 136.3, 134.7, 133.8, 133.0, 132.8, (2C), 128.8, 127.8, 123.9, 118.4, 65.0 ppm IR (neat, cm -1 ): 2360, 1705, 1633, 1491, 1170 HRMS: C 18 H 14 Cl 2 O 2 Cacld : , [M] + Found :

14 (E)-(E)-3-(4-bromophenyl)allyl 3-(4-bromophenyl)acrylate (Table 4, 5b) : The representative experimental procedure was applied to (E)-3-(4-bromophenyl)prop-2-en-1-ol 5a (106.5 mg, 0.5 mmol) to yield 5b (84.4 mg, 80 %). 1 H NMR (400 MHz, CDCl 3 ): 7.66 (d, 1H, J = 16.0 Hz), 7.52 (m, 2H), 7.45 (m, 2H), 7.39 (m, 2H), 7.28 (m, 2H), 6.64 (d, 1H, J = 15.6 Hz), 6.46 (d, 1H, J = 16.0 Hz), 6.34 (m, 1H), 4.86 (d, 2H, J = 6.4 Hz) ppm 13 C NMR (125 MHz, CDCl 3 ): 166.4, 143.8, 135.1, 133.3, 133.0, 132.2, 131.8, 129.5, 128.1, 124.7, 124.0, 122.0, 118.5, ppm IR (neat, cm -1 ): 2950, 2360, 1708, 1487, 1169 HRMS: C 18 H 14 Br 2 O 2 Cacld : , [M] + Found :

18 (E)-(E)-3-(4-fluorophenyl)allyl 3-(4-fluorophenyl)acrylate (Table 4, 6b): The representative experimental procedure was applied to (E)-3-(4-fluorophenyl)prop-2-en-1-ol (76.1 mg, 0.5 mmol) to yield (43.9 mg, 58 %). 1 H NMR (500 MHz, CDCl 3 ): 7.69 (d, 1H, J = 16.0 Hz), 7.51 (m, 2H), 7.37 (m, 2H), 7.07 (t, 2H, J = 8.5 Hz), 7.01 (t, 2H, J = 8.5 Hz), 6.66 (d, 1H, J = 15.5 Hz), 6,40 (d, 1H, J = 16.0 Hz), 6.27 (m, 1H), 4.85 (d, 2H, J = 6.5 Hz) ppm 13 C NMR (125 MHz, CDCl 3 ): 166.5, 164.9, 163.6, 162.9, 161.6, 143.8, 133.1, 132.4(2C), 130.6(2C), 130.0, 129.9, 128.2, 128.1, 123.0, 117.6, 116.1, 115.9, 115.6, 115.4, 65.0 ppm IR (neat, cm -1 ): 2361, 2336, 1716, 1509, 1158 HRMS: C 18 H 16 O 2 Cacld : , [M] + Found :

21 (E)-(E)-3-(2-methoxyphenyl)allyl 3-(2-methoxyphenyl)acrylate (Table 4, 7b): The representative experimental procedure was applied to (E)-3-(2-methoxyphenyl)prop-2-en-1- ol (82.1 mg, 0.5 mmol) to yield (47.2 mg, 58 %). 1 H NMR (500 MHz, CDCl 3 ): 8.03 (d, 1H, J = 16.0 Hz), 7.50 (dd, 1H, J = 7.5, 1.5 Hz), 7.45 (dd, 1H, J = 7.5, 1.5 Hz), 7.33 (m, 1H), 7.23 (m, 1H), 7.03 (d, 1H, J = 16.0 Hz), 6,91 (m, 4H), 6.57 (d, 1H, J = 16.0 Hz ), 6.39 (m, 1H), 4.87 (d, 2H, J = 7.0 Hz), 3.87 (s, 3H), 3.84 (s, 3H) ppm 13 C NMR (125 MHz, CDCl 3 ): 167.2, 158.3, 156.9, 140.3, 131.4, 130.1, 129.1, 129.0, 128.9, 127.2, 125.9, 125.3, 124.1, 123.4, 120.6, 120.6, 120.3, 118.6, 111.1, 110.8, 65.6, 61.7, 55.4 ppm IR (neat, cm -1 ): 3003, 2361, 1709, 1489, 1246 HRMS: C 18 H 16 O 2 Cacld : , [M] + Found :

24 (E)-(E)-3-(3-methoxyphenyl)allyl 3-(3-methoxyphenyl)acrylate (Table 4, 8b): The representative experimental procedure was applied to (E)-3-(3-methoxyphenyl)prop-2-en-1- ol (82.1 mg, 0.5 mmol) to yield (54.7 mg, 68 %). 1 H NMR (500 MHz, CDCl 3 ): 7.70 (d, 1H, J = 16.0 Hz), 7.30 (t, 1H, J = 8.0 Hz), 7.24 (t, 1H, J = 7.5 Hz), 7.12 (d, 1H, J = 7.5 Hz), 7.00 (d, 1H, J = 7.5 Hz), 6.93 (dd, 2H, J = 8.5, 2.0 Hz), 6,82 (dd, 1H, J = 8.0, 2.5 Hz), 6.68 (d, 1H, J = 16.0 Hz ), 6.47 (d, 1H, J = 16.0 Hz ), 6.35 (m, 1H), 4.87 (d, 2H, J = 6.5 Hz), 3.82 (s, 3H), 3.81 (s, 3H) ppm 13 C NMR (125 MHz, CDCl 3 ): 166.6, 159.9, 159.8, 145.0, 137.7, 135.7, 134.1, 129.9, 129.6, 123.6, 120.8, 119.3, 118.2, 116.2, 113.8, 112.9, 111.8, 65.0, 55.3(2C), 55.2 ppm IR (neat, cm -1 ): 2970, 2361, 1717, 1489, 1229 HRMS: C 18 H 16 O 2 Cacld : , [M] + Found :

26 (E)-(E)-3-(thiophen-2-yl)allyl 3-(thiophen-2-yl)acrylate (Table 4, 9b) : The representative experimental procedure was applied to (E)-3-(thiophen-2-yl)prop-2-en-1-ol 9a (70.1 mg, 0.5 mmol) to yield 9b (43.6 mg, 63 %).

27 1 H NMR (400 MHz, CDCl 3 ): 7.82 (d, 1H, J = 15.6 Hz), 7.37 (d, 1H, J = 5.2 Hz), 7.26 (d, 1H, J = 3.2 Hz), 7.18 (d, 1H, J = 4.8 Hz), 7.01 (m, 3H), 6.82 (d, 1H, J = 16.4 Hz), 6.28 (d, 1H, J = 15.6 Hz), 6.17 (m, 1H), 4.81 (d, 2H, J = 6.4 Hz) ppm 13 C NMR (125 MHz, CDCl 3 ): 166.5, 141.2, 139.5, 137.5, 131.0, 128.5, 128.1, 127.4, 126.5, 124.9, 122.7, 116.5, 64.7 ppm IR (neat, cm -1 ): 3061, 1678, 1626, 1575, 1125 HRMS: C 14 H 12 O 2 S 2 Cacld : , [M] + Found :

30 (E)-(E)-5-phenylpent-2-en-1-yl 5-phenylpent-2-enoate (Table 4, 10b) : The representative experimental procedure was applied to (E)-5-phenylpent-2-en-1-ol 10a (81 mg, 0.5 mmol) to yield 10b (21.0 mg, 26 %). 1 H NMR (400 MHz, CDCl 3 ) (major : minor = 0.6 : 0.4) : (m, 10H, 15H), (m, 1H), (m, 2H), 6.01 (d, 1H, J = 15.2 Hz), (m, 3H), (m, 2H), 4.63 (d, 0.8H, J = 6.4 Hz), 4.58 (d, 1.2H, J = 6.8 Hz), (m, 6H, 9H) ppm 13 C NMR (125 MHz, CDCl 3 ): 166.8, 166.3, 128.3, 144.8, 141.6, 140.5, 136.0, 135.3, 135.2, 129.1, 128.8, 128.5, 128.4, 128.3, 127.2, (2C), 125.9, (2C), 121.7, 121.1, 65.0, 64.9, 35.3, 34.3, 34.1, 33.9, 29.7 ppm IR (neat, cm -1 ): 3419, 1670, 1603, 1262, 1131 HRMS: C 22 H 24 O 2 Cacld : , [M] + Found :

33 (E)-(E)-2-methyl-3-phenylallyl 2-methyl-3-phenylacrylate (Table 4, 11b) : The representative experimental procedure was applied to (E)-2-methyl-3-phenylprop-2-en-1-ol 11a (74 mg, 0.5 mmol) to yield 11b (16.7 mg, 23 %). 1 H NMR (400 MHz, CDCl 3 ): 7.76 (s, 1H), 7.40 (m, 4H), 7.30 (m, 7H), 6.60 (s, 1H), 4.80 (s, 2H), 2.17 (s, 3H), 1.97 (s, 3H) ppm 13 C NMR (125 MHz, CDCl 3 ): 168.4, 139.1, 137.1, 135.9, 133.0, 129.7, 128.9, 128.4, 128.3, 128.2, 128.0, 126.8, 29.7, 15.6, 14.1 ppm IR (neat, cm -1 ): 3648, 1708, 1625, 1203, 1158 HRMS: C 20 H 20 O 2 Cacld : , [M] + Found :

36 GC analysis GC analysis conditions: Gas chromatography analysis was performed on an Agilent 6890 instrument with a FID detector and HP-5 capillary column (polydimethylsiloxane with 5% phenyl group, 30 m 0.32 mm (i.d.) 0.25 mm (film thickness) using nitrogen as a carrier gas. To analyze each sample, 50 μl of each reaction mixture was diluted with 0.5 ml of toluene and transfered to a autosampler vial. The injection volume was 1 μl and the split ratio was 100:1. The inlet temperature was 250 C, column flow was 1 ml/min (constant flow mode). The oven temperature was held at 130 C for 8 min and then increased to 250 C using 10 C/min increments. The oven was held at 250 C for 5 min, with the total run time being 25 min. GC calibration curves for cinnamyl alcohol, cinnamaldehyde, ester, and TEMPO: Tetradecane was used as an internal standard. From the chromatogram, the ratio of each compound to the internal standard was calculated. Calibration curves of cinnamyl alcohol, cinnamaldehyde, ester, and TEMPO were plotted as shown below. The area ratio of each compound to tetradecane was plotted on the x axis and the mmol of each compound on the y axis. Cinnamyl alcohol Calibration Curve

37 Cinnamaldehyde Calibration Curve Ester Calibration Curve TEMPO Calibration Curve

38 Quantitative analysis of catalytic reactions: 1) A reaction with HFIP Time (h) Cinnamyl alcohol 1a (mmol) Ester 1b (mmol) TEMPO (mmol) _ 0.500_ mmol 0.400_ 0.300_ 0.200_ 0.100_ 0.000_ 1a (mmol) 1b (mmol) TEMPO (mmol) ) A reaction without HFIP h Time (h) Cinnamyl alcohol 1a (mmol) Ester 1b (mmol) TEMPO (mmol) Cinnamalde hyde (mmol)

39 _ 0.500_ mmol 0.400_ 0.300_ 0.200_ 0.100_ 0.000_ 1a 1b TEMPO aldehyde h

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Supporting Information. Experimental section

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